CZASOPISMO POŚWIĘCONE CHEMII, TECHNOLOGII i PRZETWÓRSTWU POLIMERÓW
P O L I M E R Y
Visualization and flow velocity determination of molten
polymers
Tomasz Sterzyński1), *), Karol Bula1) DOI: dx.doi.org/10.14314/polimery.2019.9.1
Abstract: The determination of flow vectors of molten polymer by dies and mold cavities filling is a topic of many investigations, realized by various measurement techniques. The non-direct measurements are based on temperature or pressure fields determination along the flow channels, where the sensors are usually positioned in the streaming polymers, leading to flow field disturbance. The Laser Doppler Ve-locimetry (LDV) is an efficient touchless measurement technique of streaming gases and liquids velocity, deli vering directly values of the flow velocity and its direction. Principle and examples of LDV determined flow velo city distribution, are presented. The direct flow lines determination may be done by using mark-ers with a plate-like form, scanning electron microscopy (seM) observation of fractured product surface. Keywords: molten polymer flow, velocity, non-direct methods, Laser Doppler Velocimetry, flow mark-ers.
Wizualizacja oraz pomiar prędkości przepływu stopionych polimerów
Streszczenie: Pomiar wektorów prędkości przepływu stopionych polimerów przez dysze i kanały form wtryskowych stanowi przedmiot badań prowadzonych z zastosowaniem różnych technik. Pośrednie pomiary są oparte na ocenie pola wartości temperatury lub/i ciśnienia na długości kanału, przy czym czujniki z reguły są umieszczane bezpośrednio w przepływającym polimerze, co może prowadzić do zakłóceń przepływu. Laserowa ocena przepływu z wykorzystaniem efektu Dopplera w optyce (LDV) to bardzo efektywna bezstykowa metoda pomiaru przepływu gazów i cieczy, pozwalająca na określe-nie prędkości i kierunku przepływu. Opisano zasady dokonywania pomiarów oraz przykłady zastoso-wania LDV. Bezpośrednią ocenę charakteru przepływu umożliwia wykorzystanie markerów w postaci napełniaczy płytkowych w polimerze i następnie obserwacja przełomów wyrobu za pomocą skaningo-wej mikroskopii elektronoskaningo-wej (seM).
Słowa kluczowe: stopiony polimer, przepływ, metody pośrednie, laserowa ocena przepływu z wyko-rzystaniem efektu Dopplera w optyce (LDV), markery przepływu.
The final properties of polymeric products fabricated by techniques, like injection molding, extrusion, com-pression molding and others, beside material selection
and its composition, are significantly macromolecular orientation dependent. This effect is widely known and described in papers where as well the anisotropic effects
1) Poznan University of Technology, institute of Materials Technology, Piotrowo 3, 60-965 Poznań, Poland.
[1, 2] like elastic modulus and elongation, anisotropy of the heat transfer [3, 4], as well as changes of thermal pro-perties, like melting temperature by semi-crystalline po-lymers [5, 6], due to significant macromolecular orienta-tion.
Consequently, to find how the physical properties are influenced by macromolecular orientation, and/or pri-vileged positon of polymeric chains, several structure related investigations, like wide-angle X-ray scattering (wAXs), differential scanning calorimetry (DsC), scan-ning electron microscopy (seM), atomic force microscopy (AFM) are habitually used. in this case a special procedu-re of sample pprocedu-reparation is needed. Most fprocedu-requently tech-niques used for sample preparation, for structure deter-mination are: micro cuts of microscopic samples, cutting of mg-like samples for DsC, as well as creation of special forms, like film with a micrometric thickness, or etching [7] for samples where the spherulitical morphology on the surface will be detected. The main task by all these investigation methods, is the observation of structure in the final products and in specially prepared samples. To complete the structure characteristic, especially in sam-ples and products with larger thickness, special procedu-re like gradient dependent investigation has to be applied [8]. An alternative way allowing to follow the structure formation during polymers processing is the molten flow visualization, by means of optical studies of the flow li-nes. This methods are known since years, although due to certain restrictions and experimental concerns, still in development.
FLOW VISUALIZATION BY BIRKS AND BAGLEY Bagley and Birks published in 1960 [9] the flow lines of molten polyethylene at the capillary entrance, using a new technique for visualization, of flow patterns below and above the critical value of shearing stress, leading to distorted stream of extruded molten polymer. it allowed to observe directly the melt flow above the capillary en-trance, and to determine the rate at which the energy in the flow may be dissipated, resulting in a steady flow into the capillary (Fig. 1).
The usage of temperature and pressure sensors, posi-tioned directly in the streaming polymer may, also serve to determine indirectly the molten flow velocity of po-lymers by passing the channels or the dies. several re-striction have to be taken into account by these measu-rements, particularly the ratio between measurements receptivity and short response time vs. mechanical re-sistance of sensors, sufficiently negligible distortion of the flow of molten polymers, due to the sensors placed directly in streaming melt, as well as appropriate ther-mal resistance of the measuring system. As a temperatu-re gradient is normally observed in the molten polymer flow [10], to gain the knowledge of the entire temperature field on the cross section of the flow, the sensors must be displaced along the die/channel radius, thus special sys-tems are needed in this case [11–13].
The positron emission particle tracking was applied by [14] to visualize the flow of a polymeric composite in twin-screw extruder, in realistic processing conditions. The residence time and residence time distribution in screw sections, like kneading part, conveing and re-verse elements was compared with numerical particle tracking.
THE TOUCHLESS OPTICAL FLOW VELOCITY MEASUREMENTS
The arrangement and orientation of additives in form of fibers, by flow of polymeric composites inside the
ori-fice narrow channels, was studied by means of
visualiza-tion and numerical evaluavisualiza-tion [15]. The determinavisualiza-tion of fiber angle variation along the flow channel, in different initial locations of the fiber, allows to conclude that by using of such method, a better understanding of flow in-duced anisotropy of physical properties of composite may be achieved.
The way to follow the homogenization process in the case of a composite of low density polyethylene with car-bon black was published by wong et al. [16–20], where also another observations obtained by this visualization technique are reported. The dynamic mixing in a single
screw extruder was observed by using a window
moun-ted directly in the extruder barrel. The time dependent mixing process and its fluctuation as a function of screw velocity, i.e. residence time were observed, where also the screw rotation speed, leading to the best mixing quality, was determined.
The quality of twin-screw extrusion mixing of polymer blends, composed of various ratio between polypropyle-ne (PP) and polystyrepolypropyle-ne (Ps) parts, was studied by [21]. The direct flow observation, using of a glass window in-corporated in the twin-screw barrel, allows to realize the online visualization of the quality of mixing procedure of these two polymers.
The direct visualization of molten polymer flow, by means of optical windows fixed in the injection mold, have also been published. Masato et al. [22] have studied the flow of polystyrene in an injection mold with low--friction mold surface coatings. Particularly, the flow of polymer in the thin-wall parts, causing the wall slip ef-fect, has been observed by use of a mold with sapphire windows. A high-speed visualization during the filling phase, and the measurements of velocity distribution across the cavity thickness allowed to confirm the ab-sence of the typical “fountain-flow” in this particular case. On the contrary, the importance of the adhesion at the polymer-mold interface was demonstrated by means of measurements of contact angle of molten polystyre-ne across the considered mold surface coatings, showing that the value of angle was inversely proportional to the melt flow resistance.
An interesting and valuable visualization of instabili-ties in polymer flow was proposed by Nabiałek [23], by investigations of polymer flow during cavity filling pha-se. in this case a dedicated injection mold which enables the observations and video recording of the in situ flow of the molten polymer, has been used. The direct moni-toring of the streaming polymer inside the mold cavity in two planes was realized by means of a transparent sight-glasses, made of the glass ceramic zerodur [24], characterized by the nearly zero coefficient of thermal expansion. To record the stream direction, a digital video camera has been employed, allowing to described the ef-fect of polymer flow around the rectangular obstacle at the cavity, as well as the jetting phenomena.
A very simplified validation of particles orientation was proposed by rajasekaran et al. [25], based on de-termination of natural fiber orientation during flow in transparent mold cavity, and by the numerical and expe-rimental approach to evaluate the flow phenomena. A si-licone resin, as a viscous fluid and natural filler – short coconut fibers with an average length of 2 mm, were applied in these investigations. The cavity filling steps during silicone/coconut fiber injection were recorded by a digital camera, and the numerical calculations were done by considering fluid elements and predicted an-gular velocity of laminar flow. The Authors described the shape parameter as a fiber curling factor, in the case when the coconut fibers are not enough stiff and reve-aled curled effect. The angle of coconut fibers orientation
was validated by the assumption that the polymer flow front induce an impulse moment on short fiber and she-ars short fiber to rotate with respect to fiber geometrical center (Fig. 2).
The rajasekaran researcher group found that fibers move with rotational and translation motion during fil-ling of cavity, an effect in a good agreement with the-ory of flow. The numerically predicted orientation allow to conclude that the proposed model was validated with experimental data.
THE LASER DOPPLER VELOCIMETRY OF MOLTEN POLYMERS FLOW
The most effective way to determine the flow velocity of gases and liquid systems are the direct measurements by means of laser Doppler velocimetry (LDV), called also laser Doppler anemometry (LDA) [26]. This widely used technique in the case of flow measurements in turbine systems is based on the Doppler principle in optics. One of the main benefit of LDV is the possibility to realize the measurements of the flow velocity of gases and liqu-ids touchless, i.e. only a laser beam is positioned in the stream, thus a principle of non-distortion of the flow is fulfilled. By the LDV measurements the velocity vector with its value, direction, turn and local position may be touchless determined, thus the LDV experiments may de-liver significant information’s necessary to design chan-nels and dies in many industrial applications, allowing to optimize the flow pathway of practically all streaming mediums.
in 1964, LDV was employed for the first time by Yeh and Cummins [27] for measuring the velocity profiles of streaming water. Due to the relatively complex design of LDV measurement systems, particularly in the case of molten polymers flow determination where experiments with the use of thermally resistant optical systems sho-uld be used, its description may be found in few papers [28–32].
The setup and the way to realize the measurements of the molten polymer flow by LDV was published by [33]. similarly as in [27–31] the Authors have used a slit die with a planar contraction of 14 : 1. The investigation of the velocity fields was performed in the steady state of flow. The optics of the LDV system was reliable for measure-ments of even very low velocities. To improve the signal
Flow front Fiber Mass center Relativ e velocity Rotation Flow front Uniform distribution of velocities Relativ e velocity
ror of few percent, i.e. lower comparing with the measu-rements of the volume flow rate. The viscosity functions were obtained by measuring over a wide range of shear rates, using the velocity profile by fully developed flow in the slit die, checked additionally by measurements done with a capillary rheometer.
The Authors have concluded their research with a sta-tement that the LDV setup is a powerful experimental tool to investigate the flow behavior of polymer melts, and its accuracy and high spatial and temporal resolu-tion opens a way to get more quantitative insight into the flow of polymer melts, and to check the validity of certain model calculations.
The entry flow of low-density polyethylene was deter-mined by laser Doppler velocimetry by wassner et al. [34]. The measurements were realized by using an experimen-tal extrusion set with a slit die, where the flow velocity was measured. This highly developed measurement technique was used also to determine the secondary flow of the po-lyolefins melts depending on its molecular structure [35].
The volumique defects appearing during extrusion were discussed in the paper published by Combeaud and other [36], based on the measurements of molten po-lystyrene flow. These experiments were realized simul-taneously by birefringence and laser Doppler velocime-try. An analogous experimental set, i.e. instantaneously birefringence and LDV measurements were employed by schubert and Muenstedt [37] for the determination of the stress and flow velocity distribution on the cross section of the channel.
in the papers from Hertel and Muenstedt [38, 39] the influence of the processing parameters on the secondary flow of polyethylene, measured by LDV by the three di-mensional entrance flow of LDPe and LLDPe into a slit die, are presented.
Burghelea and others [40] have described an experi-mental study of the physical origin and the mechanisms of the sharkskin instability. Two polymers, i.e. a linear low density polyethylene (LLDPe) which exhibits shark-skin instability, and a low density polyethylene (LDPe) which does not show any instability over a broad range of flow rates, were investigated by combining the laser
Doppler velocimetry (LDV) within a slit die with rheolo-gical measurements in both uniaxial extension and she-ar flow. The principle of the laser Doppler velocimetry measurement technique is presented on Fig. 3. The laser beam radiation is splattered on two beams, where by one of them, by passing through a Bragg cell, a defined shift of light beam frequency is achieved [26–29, 33].
The two beams are focused passing by the lens, and create a measurements volume with the dimension of some micrometers, which may vary depending on the angle between the beams focused by the lens, and the distance between the lens and the measured flow (Fig. 4).
in case of the LDV measurements in the flow of molten polymers, due to the relatively high temperature of the streaming medium, the distance between the optical sys-tem and the extrusion die may not be too short [28, 29, 33]. The creation of the back-scattered light is essential to ful-fill the necessary conditions of the Doppler effect in case of measurements of streaming medium. Therefore, usual-ly the micro particles, like for example TiO2 [28, 29, 33], are dispersed in the liquid, in our case in the molten polymer. such LDV measurements are restricted due to some technical difficulties, like the necessity to use an extrusion die with transparent wall in a form of glass windows, re-sistant against the high temperature and assuring a tigh-tens for the flow of molten polymers. Another significant condition is the achievement of a high transparency for the optical beam, even in application of molten polymer processing, i.e. the light refraction coefficient should be as low as possible. in this case the most favorable results [23, 28, 30] were completed by using the zerodur [24], a special low thermal expansion glass ceramic for special optical applications. The zerodur may relatively easily be formed mechanically, possessing the necessary thermal resistance and optical properties. As stated already abo-ve, the additional requirement in case of molten polymer flow determination is a high temperature resistance of the glass window, combined with the tightens of the extru-sion/injection molding molten polymer flow.
As mentioned before the ability to perform the flow ve-locity measurements in a touchless mode, it means without introducing the sensors into the streaming medium, is the
Laser Lens Particle Light detector Lens Flow with particles Beam splitter
Fig. 3. The principle of laser Doppler velocimetry measurement technique [26–29, 33]
beam 2 beam 1
n
Fig. 4. The measurements volume created by focused laser beams with the interference lines
main advantage of LDV. Another appreciated factors are the very small dimensions of the measurement volume, relatively to the cross section of the streaming medium. On this way relatively easy the flow velocity distribution on the cross section of the channel/die, may be measured and established [31]. This, in turn allows to measure the flow at the positions even very close to the die wall, whe-re a significant shearing in the stwhe-reaming molten polymer occurs (Fig. 5). On Fig. 5 the flow velocity on the cross sec-tion of the die is presented, at the posisec-tion of 30 mm after the entry to the die from the reservoir. in this case a ful-ly developed flow is characterized by relativeful-ly wide core section without shearing, and the near wall part where the shearing of the molten polymer is predominant.
By the LDV measurements the velocity vector is deter-mined at the surface normal to the optical axis of the LDV system, thus, adjusting the LDV system also the velocity vectors in the direction perpendicular to the flow axis may be measured. such determination of the velocity vectors in the radial directions (secondary flow) may par-ticularly be important, when the flow reaches the high reynolds values, what is usually not the case by molten polymers streaming.
THE MICROPLATE-LIKE ADDITIVES AS FLOW MARKERS
The usage of microplate-like additives, introduced into the molten polymer, serving as flow lines markers presents another relatively simple method employed to determi-ne the flow of molten polymers. Talc and/or mica are the mostly used additives in this case. The first experimen-tal stage by this technique is the preparation of composi-tes of investigated thermoplastic material charged with a defined quantity of plate-like additives. On Fig. 6 the talc particles with a mean particle diameter of 3 µm, are
presented [41]. such method was already used by [42, 43] and various extrusion/injection molding processing con-ditions may be investigated by means of this technique. The flow lines estimation is performed by microscopic observations of the cross section of the extruded/injection molded products.
A comparable way for multiple cavity filling visuali-zation procedure was chosen by Bociąga et al. [44, 45]. in these investigations also the talc-filled low density po-lyethylene was used for the flow lines visualization, in an injection mold with multiple cavities. The microsco-pic observations were performed on the cross-section of the runners and of the mold cavity using slices cut per-pendicular to the flow direction. The observations were realized by means of optical microscopy with polarized transmitted light, and the allocation of the talc plates was analyzed by scanning electron microscopy (seM). it was stated that the molten polymer does not fill all mold cavities at the same time, what probably may be due to changes of the direction of polymer flow in runners. According to previous experiments [41], we have found that 10 wt % is the best concentration of the plate-form markers, and mica as the marker is less convinced for such investigation, as the mica additives are hardly visi-ble at the cross section of the polymeric products.
An observation of a characteristic molten polymer “fo-untain flow” during mold cavity filling, was published before [41]. it was shown that various forms and dimen-sional relations of the flow lines distribution exist, where independent on the filling conditions, a “fountain flow” effect was confirmed. Depending on the cavity thickness, a clear distinction of at least three flow lines orientation regions, on the cross section of the product, were obse-rved.
At the skin layer, near the wall part of the flow, a direc-tion oriented alignment of makers may prove a signifi-cant shear flow of molten polymer, existing in this chan-nel zone. At the core of the flow, a perpendicular position of the markers, relatively to the filling flow direction, si-gnify a “fountain flow” at the middle axis of the cavity (Fig. 7). At the region between the core and the near wall
0.4 0.2 0.0 -0.2 -0.4 measurement power law fit: n = 0.36 y-position, mm LDPE V= 0.40 cm /s3 T= 180 °C z= 0 mm x= 30.0 mm 40 35 30 25 20 15 10 5 0 V elocity ,mm/s Vx
Fig. 5. The LDPE flow velocity distribution on the cross section of a die; comparison of LDV measurements with power low fit for n = 0.36; the measurements were realized across the section of a die at the positon of 30 mm after the entry from the reservoir to the die [39 similar results at 30–32]
20 m
Fig. 6. SEM image of talc particles Naintzsch A10 (from Luzenac) [41]
part, an intermediate alignment of the markers is well visible, an effect which approve a filling of the cavity by a fountain-like flow [41, 43–45].
in our previous investigations [46], the composites with the markers were considered to study the flow lines, and consequently the macromolecules positon by filling a mold cavity with metal inserts. in the view of growing production of the light constructions, used in automotive, aircraft and other industrial applications, such injection molding products, shaped with a strong adhesive bon-ding of metallic with polymeric parts, are gaining an im-portance today. special requirements by growing techni-cal applications of light-construction is the reason of the importance of new developments by such metal-polymer connections, achieved without any additional mechani-cal coupling, nor by the use of any technimechani-cal glue.
MARKERS TYPE POLYPROPYLENE FLOW DETERMINATION AT THE CAVITY ENTRANCE
The polypropylene HP 500N (Basell Orlen Polyolefins, Plock, Poland, MFR = 12 g/10 min) was applied as matrix of the composites. Commercially available talc extra 10 (purchased from Aurum Chemicals, Katowice, Poland) was used as flow markers. The composites of PP with talc were produced by extrusion, using a zAMAK twin--screw extruder, operating at the temperatures betwe-en 165 °C and 205 °C along the barrel, by screw rotation speed of 150 rpm.
The injection molding was realized by means of engel HLs 80/20 injection molding machine, with the barrel temperature between 185 °C and 220 °C, operating by fol-lowing processing parameters: hydraulic filling pressure 10 MPa, hydraulic packing pressure 7 MPa, packing time 4 s and cooling time 25 s. The polymer/metal connection parts were produced using a mold presented on Fig. 8.
On the microscopic observations of the cross section of injection molded part, the segment of the mold inlet may be seen (Fig. 9). The observed area is focused on the place where the cross section of the flow abruptly increases, ga-ining a double thickness comparing to the channel,
cau-sing a local disorientation of the polymer flow arrange-ment. in this particular area the flow lines of the melted polymer with plate-like particles may be seen. This area is particularly of interest because of well seen polymer flow lines with easily detected talc particles allocation. The brittle behavior of sample fracture allows us to loca-lize the side view of the narrow edge on the top surface of platelet particles, as visible markers of macromolecules flow path during channel/cavity filling. Once again talc – as a flow marker was successfully used for quantifica-tion of orientaquantifica-tion/disorientaquantifica-tion of polymer structure in micro and macro-scale observation.
As it follows from Fig. 9, a significant change of the flow induced orientation of the marker, therefore of the macromolecules by passing the sharp edge of the cavity inlet, may be clearly observed. The primary flow direc-tion alignment of the markers is strongly influenced by an extension of the flow cross section (Fig. 9 b) leading to an almost perpendicular flow regarding the main filling direction. shortly after, an alignment of markers again in the main flow direction (Fig. 9 c) results in significant macromolecular orientation, as usually observed [46] in the case of alongside filled cavities.
Fig. 7. SEM images of cross sections of a 1 mm thick injection molded part made of LDPE 10 wt % of talc [41]
Fig. 8. Top view of injection mold cavity with localization of ob-served inlet gate with thickness of 1 mm
Fig. 9. SEM pictures of: a) brittle fractured sample (PP/10 wt % of talc), b) magnification of selected area, c) location of talc particles, (abbrev. FD – flow direction)
CONCLUSIONS
we have presented several methods of observation of mold cavity filling by thermoplastic polymers. such inve-stigations are now-a-days very important due to signifi-cant influence of orientation on the products properties. This dependence is particularly worth in a case if isotro-py and/or anisotroisotro-py may be decisive by polymeric pro-ducts applications.
Few methods of flow visualization have been presented and briefly discussed in this paper. The direct flow detec-tion, what is the case by laser Doppler velocimetry, provi-des exact values of the velocity vectors at channels, cavities
etc., thus may be very profitable for the designing of
mol-ten polymer flow, as well as may be applied for the verifi-cation of rheological models. From this point of view the LDV presents a very important technique, currently used for the designing of turbines, flow meters etc. The main difficult although is the high cost of such equipment and a long time necessary to establish the measurement system.
The microscopic observation of the cross section of po-lymeric products filled with flow markers, presents on the contrary a very simple, low cost and multipurpose universal method, delivering the information’s about the flow lines distribution on the section of the streaming polymer. such information’s are in many cases sufficient for the validation of the mold cavity filling simulations, and/or prediction of the local positioning of the macro-molecular structure, thus giving data’s of possible struc-ture/properties anisotropy.
ACKNOWLEDGMENT
This work was supported by the National Scientific Center (NCN) in a frame of Grant OPUS 2016/21/B/ST8/03152, what is greatly acknowledged.
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[46] Bula K., szymańska J., sterzyński T. et al.: Polymer
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http://dx.doi.org/10.1002/pen.25047
Received 19 IV 2019.
INSTYTUT INŻYNIERII MATERIAŁÓW POLIMEROWYCH I BARWNIKÓW w TORUNIU
ODDZIAŁ FARB I TWORZYW w GLIWICACH
zaprasza do udziału w Xiii Międzynarodowej Konferencji
ADVANCES IN PLASTICS TECHNOLOGY
(POsTĘPY w TeCHNOLOGii TwOrzYw POLiMerOwYCH) Chorzów, 29–31 października 2019 r.
Tematyka Konferencji:
• Nowości w zakresie bazy surowcowej do produkcji tworzyw: materiały polimerowe (żywice, mieszanki do
formowania, polimery biodegradowalne, nanopolimery), kompozyty i nanokompozyty polimerowe, pigmenty i barwniki, koncentraty polimerowe, napełniacze i dodatki wzmacniające, środki pomocnicze i modyfikatory
• Osiągnięcia w zakresie przetwórstwa tworzyw i ich stosowania
• Nowoczesne rozwiązania dotyczące maszyn i oprzyrządowania w przetwórstwie tworzyw
• Ochrona środowiska naturalnego, recykling, regulacje prawne
• Zagadnienia badawcze i rozwojowe oraz kontrolno-pomiarowe
• Trendy rynkowe
Język konferencji: angielski i polski (symultaniczne tłumaczenie). Czas prezentacji referatu – 25 min. (wraz z dyskusją).
Opłata konferencyjna: 1 000 zł + 23 % VAT
Termin przysłania tytuł referatu lub plakatu (w j. angielskim i polskim), skrótów (do 120 słów) oraz biografii autora (do 50 słów w j. ang.) – 31 maja 2019 r.
Termin przysłania pełnych tekstów wystąpienia (do 10 stron formatu A-4 w j. ang.) – 30 sierpnia 2019 r.
Jest możliwość promocji firmy w formie wkładki reklamowej, plakatu lub stanowiska promocyjnego podczas kon-ferencji.
Miejsce konferencji: HOTeL GOrCzOwsKi, Chorzów, ul. stefana Batorego 35
Informacje: mgr inż. Anna Pająk, Maria Błach, instytut inżynierii Materiałów Polimerowych i Barwników Oddział Farb
i Tworzyw, ul. Chorzowska 50A, 44-100 Gliwice, tel. +48 (32) 231 9043; fax: +48 (32) 231 2674; e-mail: a.pajak@impib.pl
